The grafting of 4-nitrophenyl groups on carbon or metallic surfaces without externally applied electrochemical induction is described. Clean surfaces of glassy carbon (GC), copper, nickel, iron, and zinc substrates were dipped in a solution of 4-nitrobenzene diazonium tetrafluoroborate salt in acetonitrile. After the modified surfaces were rinsed, they were analyzed by FT-IRRAS, cyclic voltammetry, XPS, and AFM. The main result of this investigation is the spontaneous formation of a multilayer coating without electrochemical induction regardless of the substrate used. Influence of immersion time and of 4-nitrobenzene diazonium tetrafluoroborate salt concentration on the grafting were also investigated.